FI58511B - TVAETT- OCH RENGOERINGSMEDEL INNEHAOLLANDE STOEDSUBSTANSER - Google Patents

Description

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National Board of Patents and Registration (44) Publication and date of publication. - 0

Patent and registration authorities AmBkan utlafd och i / tUkrtfun pubitearad 31.10.80 (32) (33) (31) Pyydatty «tuolkaui —Bafird prior It at 28.05.73

Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 23271U1.2 (71) Hoechst Aktiengesellschaft, Frankfurt / Main, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (72) Wilhelm Vogt, Hiirth-Efferen, Eberhard Auer, Erft

Gunter Lenz, Frechen-Bachem, Karl Merkenich, Hiirth-Efferen,

Klaus Henning, Hurth-Hermiilheim, Joachim Kandler, Erftstadt Lechenich, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (7U) Oy Kolster Ab (5U) Detergents and cleaning agents containing structural salts - Tvätt- och rengöringsmedel innehällande stöds

The invention relates to detergents and cleaning agents which contain, as structural salts, water-soluble salts of copolymers of? -Hydroxyacrylic acid and acrylic acid.

It is known that the cleaning performance of soaps and synthetic detergents in detergents can be improved by adding certain products that reduce water hardness. Such detergents are called structural salts. Detergents and cleaners containing structural salts are more effective and still less expensive than the corresponding mixtures without structural salts.

In addition to the non-ionic surfactant portion of the detergent composition, which only disperses and / or peptizes hydrophobic dirt, such as soot and grease particles, the detergent must also contain an ingredient suitable for removing hydrophilic dirt. Structural salts are used for this. In the absence of such a structural salt, 1> V ".

2,58511 The washing solution only imperfectly binds the soiled dirt in the laundry during the washing process, so that the dirt particles settle into the laundry and a satisfactory washing performance is not achieved.

The mechanism of action of structural salt and its details have not yet been fully elucidated. Several events have an impact on the function of structural salts. These include the stabilization of pigment sludge suspensions in the washing solution, the emulsification of dirt particles, the effect of the surface and interface properties of aqueous surfactant solutions, the solubilization of water-insoluble particles in the washing solution, the peptization of dirt agglomerates, the neutralization of inorganic substances and neutralization of acidic substances.

In order to determine the efficacy and suitability of various products as structural salts, it is appropriate to study not only their ability to bind Ca ions and their ability to form stable dispersions, but also their behavior and amount of effect in the washing or cleaning process itself. In this way, it can be ensured that all the factors involved in the structural salt effect are taken into account both qualitatively and quantitatively.

Previously known structural salts include water-soluble alkali metal salts of mineral acids, such as alkali metal carbonates, borates, phosphates, polyphosphates, hydrogen carbonates and silicates.

Of the numerous products proposed for use as structural salts, straight-chain condensed alkali phosphates, especially sodium tripolyphosphate, are used almost exclusively in ordinary detergents. Detergents contain up to about 50% by weight of these structural salts.

As a result of the significant increase in the use of phosphate-based detergents and cleaners in both households and industry, the phosphate content of natural waters has also increased. In discussing the reasons for the increasing nutrient content of waters, it has recently been explicitly argued that water-soluble nitrate and phosphate salts are characterized, under certain conditions, by promoting the growth of certain algal species and contributing to this pathway by increasing the nutrient content of the water. Although an unambiguous account of the contribution of phosphate-based detergents to the increase in nutrients in water is currently not available, efforts are needed to develop effective nitrogen- and phosphorus-free substitutes for the structural salts hitherto used in detergent compositions.

It is already known to use nitrogen-free and phosphorus-free structural salts in detergent compositions. As such, for example, starch derivatives such as dicarboxylic and carboxymethyl starch or carboxylic acid polymers such as polymaleic acid and polytaconic acid, as well as copolymers of unsaturated carboxylic acids, olefins or short-chain carbohydrates or olefins or copolymers thereof have been used. Oxidic acetic acid, oxydisuccinic acid, cyclocarboxylic acid such as benzenepenta- or tetracarboxylic acid, polyethylene glycol and adipic acid ester, maleic acid with sulfonate groups, and ethylene-glycol and triethylate glycol and triethylate glycol and triethylacetol and triethylate glycol triethylate have also been proposed for use as structural salts. In addition, it is known from DE-A-2 136 672 and 2 161 727 and from a publication by P. Berth, G. Jakobi and E. Schmadel in Chemiker-Zeitung 95 (1971), pages 5 ^ * 8-553, that in the detergents, poly-hydroxyacrylic acid or polyacrylic acid or their alkali metal salts are used as structural salts.

The above-mentioned substances have not proved to be satisfactory structural salts in all respects, since these substances do not have a sufficient number of the structural salt properties initially investigated and thus do not give satisfactory washing results. To date, there have been no economic methods for preparing these compounds. The above-mentioned drawbacks characteristic of known structural salts do not exist as structural salts according to the invention.

It has now surprisingly been found that a copolymer of α-hydroxyacrylic acid and acrylic acid, or a corresponding sodium salt, has substantially better sequestration than polyvalent metal ions than, for example, poly-o-hydroxyacrylic acid or polyacrylic acid or their alkali or alkali metal.

The invention thus relates to detergents and cleaning agents comprising anionic, cationic, zwitterionic, ampholytic and / or nonionic surfactants and, if appropriate, other additives which are known to contain from 10 to 90% by weight of structural salts. o <-hydroxy i Water-soluble salts of acrylic acid and acrylic acid mixed polymers having an acrylic acid content of 9 to 85 mol / l and having a relative viscosity measured as a 1% by weight solution in 2N aqueous NaOH At ° C is from about 0.05 to about 1.0.

The lime-binding capacity of the copolymer according to the invention is considerably higher than would be expected stoichiometrically, i. the copolymer has an unexpected synergistic effect. This result is all the more astonishing because, according to the researchers P. Berth, G, Jakobi and E. Schmadel, Chemiker-Zeitung 95 »(1971)» pp. 5 ^ 8-553, it is known that the lime-binding capacity of polyacrylic acid corresponds relatively closely to a stoichiometrically calculated ratio. . By using partially cheap acrylic acid in the preparation of the mixed polymer, its production cost is substantially reduced as compared with the production cost of poly-hydroxyacrylic acid. These copolymers should therefore be selected for use as structural salts in detergents and cleaners.

It has proved particularly advantageous to use water-soluble salts of copolymers prepared from o <-hydroxyacrylic acid and acrylic acid, such as, for example, alkali or ammonium salts, as detergent and cleaning agent components.

Detergents and cleaners may contain the structural salts of the invention in an amount of about 10 to 90% by weight, especially 20 to 60% by weight.

The detergents and cleaners of the present invention include anionic, cationic, zwitterionic, ampholytic and / or nonionic surfactants, and optionally other additives, characterized in that the acrylic acid content of the copolymers of o-hydroxyacrylic acid and acrylic acid is about 9-85 molar # preferably 16-50 molar # and having a relative viscosity of about 0.05 to about 1.0, preferably 0.1, measured as a 1 wt% solution in 2N aqueous NaOH at 20 ° C. -0.8.

The detergents and cleaners according to the invention may also contain previously known structural salts, such as, for example, alkali polyphosphates. It is preferred to use anionic or nonionic substances as surfactant components in the detergent.

By anionic surfactants is meant water-soluble salts of higher fatty acids or rosin acids, such as hardened or uncured coconut palm kernel or turnip oil, and sodium or potassium soaps of tallow and the like. The anionic active compounds according to the invention also also mean alkyl-substituted, monocyclic aromatic sulfonates, such as alkylbenzenesulfonates having an alkyl residue of 9 to 11 * carbon atoms, alkyltoluene sulfonates -hexadecyl sulphate, triethanolamine lauryl sulphate, sodium or potassium oleyl sulphate, and sodium or potassium salts of lauryl sulphate ethoxylated with about two to six moles of ethylene oxide and the like.

Nonionic surfactants for detergents generally refer to compounds having an organic hydrophobic group and a hydrophilic residue. Examples of such nonionic surfactants are condensates of alkylphenols and ethylene oxide or higher fatty alcohols and ethylene oxide, further condensates of polypropylene glycol and ethylene oxide or propylene oxide, and reactants of ethylene oxide with ethylenediamine and propylene oxide. The group of compounds mentioned above also includes long chain tertiary amine oxides. The following compounds which are ampholytic or zwitterionic in nature are also suitable for the use of the tenside component of the detergents according to the invention: derivatives of aliphatic, secondary and tertiary amines or quaternary ammonium compounds having 8 to 18 carbon atoms in the aliphatic residue a phenyl group such as sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, 3- (N, N-dimethyl-N-hexadecylamino) -propane-1-sulfonate or fatty acid amidoalkyl-N, N-dimethylacetobetaine, wherein —18 C atoms and 3 C atoms in the alkyl residue.

Other additives which may also be present in the detergents and cleaners according to the invention include, for example, alkali or ammonium salts of sulfuric acid, silicic acid, carbonic acid, boric acid, alkylene, hydroxyalkylene or aminoalkylenephosphonic acid, . Separately listed, the latter groups of compounds include sodium perborate mono- or tetrahydrate, alkali salts of peroxy-mono- or diric acid, peroxo-hydrates of ortho-, pyro- and polyphosphates, water-soluble precipitated magnesium silicate and nitric acetic acid nitric acid, and iminodiacetic acid, iminodiacetic acid.

Detergents and cleaners may also contain additives which improve the soil release capacity of the washing solutions, such as carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone or substances suitable for controlling foaming, such as desiccants, mono- and dialkylphosphoric acid esters with alkyl substances and / or proteolytic enzymes.

The structural salt-containing detergents and cleaners according to the invention are to be regarded as technical advances, since they substantially prevent or retard the precipitation of calcium ions in the washing solution and, in addition, form stable dispersions with both hydrophilic and hydrophobic dirt particles. An additional advantage is that the structural salts used do not contain any phosphorus or nitrogen and thus do not contribute to an increase in the nutrient content of natural waters. The lime-binding capacity of the copolymers contained in the detergents according to the invention surprisingly exceeds more than twice the stoichiometrically calculated value, whereas in the case of poly-acrylic acid or its sodium salt, the stoichiometrically calculated lime-binding capacity is approximately equal. Slightly more advantageous than in the case of polyacrylic acid are the conditions in the case of poly - <* - hydroxyacrylic acid, in which case, however, there is a clear difference from the structural salt according to the invention.

The invention is further illustrated by the following examples, in which Examples 1-6 describe the preparation of structural salts related to the invention, while Examples T and 8 describe the function of structural salts in terms of lime binding capacity or in a washing test in the presence of other detergent components.

Example 1

A mixture of 213 g (2 moles) of o <-chloroacrylic acid and 1.5 liters of benzene was heated in a polymerization vessel to 80 ° C, and 1 g of benzoyl peroxide was added to the mixture. 72 g (1 mol) of acrylic acid were then added dropwise to the mixture with stirring over a period of 30 minutes. After an additional 2 g of benzoyl peroxide was added to the mixture, it was allowed to stand at 80 ° C for 5 hours, after which it was cooled and the polymer was filtered off and dried. 286 g of a copolymer with a chlorine content of 2U, 1 # were obtained. Taking into account the fact that some HCl gas was released during the polymerization, the acrylic acid content of the copolymer was 3 .mu.mol. The relative viscosity of the 1 weight percent solution of polymer in dimethylformamide at 25 ° C was 0.63.

To prepare the copolymer from β-hydroxyacrylic acid and acrylic acid, 80 g of the chlorine-containing copolymer described above was mixed in 800 ml of boiling water, and the mixture was boiled with vigorous stirring for 3 hours. The precipitated fine hydrolyzate was filtered off and dried. The yield was 55 g.

The relative viscosity of the 1% by weight solution of the polymer dissolved in 2N aqueous NaOH was 0.3%.

Example 2

A mixture of 213 g (2 moles) of o-chloroacrylic acid, 1 UU g (0.2 moles) of acrylic acid and 2 liters of Essovarsol® product (Esso mineral oil fraction with a boiling range of 11 + 1 + -175 ° C) was heated in a polymerization vessel at 80 ° To C and then 2.13 g of benzoyl peroxide was added. The mixture was stirred for 5 hours at 80 ° C and after cooling the polymer was filtered off. The polymer was washed with low boiling petroleum ether and dried. 222 g of polymer with a chlorine content of 28.6% and an acrylic acid content of 9 mol% were obtained.

7,585,11 g of the polymer described above were mixed with 1.5 liters of boiling water and converted according to Example 1 into a polymer containing O-hydroxyacrylic acid. The yield was 86 g. The relative viscosity of a 1% by weight solution of the polymer dissolved in 2N aqueous NaOH at 20 ° C was 0.15 ·

Examples 3 ~ 5

The procedure was the same as in Example 2, except that the amount of acrylic acid used and the amount of catalyst were changed. The test results obtained are summarized in Table 1,

table 1

Example_3_J * _5_ A 28.8 72.0 1UU, 0 B 2.13 3.0 3.6 C 236.0 280.0 353.0 D 26.7 22.5 18.3 E 17.0 3fc, 0 50.0 F 0.57 0, U8 0.52 G 89.0 97.0 101 *, 0 H 0.20 0.30 0.36 A = amount of acrylic acid used (g) B = amount of benzoyl peroxide ( g) C = yield of chlorine-containing copolymer (g) D = chlorine content of the copolymer (1 #) E = acrylic acid content of the chlorine-containing polymer (molar #) F = relative viscosity of a 1% by weight solution of chlorine-containing polymer in dimethylformamide at 25 ° C G = yield of hydrolyzed copolymer (g) Relative viscosity of a 1 weight solution of hydrolyzed polymer dissolved in H = 2 n aqueous NaOH at 20 ° C.

Example 6 213 g (2 moles) of N-chloroacrylic acid were dissolved in 7.5 liters of Essovarsol® in a polymerization vessel and the solution was heated to 80 ° C. After 3.5 g of benzoyl peroxide was added thereto, 720 g (10 moles) of acrylic acid were added dropwise over 3 hours with vigorous stirring.

In addition, benzoyl peroxide was added four times in 1.5 g portions at hourly intervals. After a reaction time of 8 hours, the polymer was filtered off, washed with low boiling petroleum ether and dried.

5851 1 8

938 g of a polymer with a chlorine content of 7.5 # were obtained. The proportion of acrylic acid was 81 * mol. The viscosity of the 1 wt.% Dimethylformamide solution of the copolymer at 25 ° C was 0.79.

To hydrolyze the copolymer, 80 g of the copolymer was boiled for 3 hours in a liter of water. The solution was then evaporated to dryness. The yield of the hydrolyzate was 69 g. The viscosity of a 1 wt.% Solution of polymer dissolved in 2N aqueous NaOH at 20 ° C was 0.55 *

Example 7

The calcination capacity (KTV) of the hydrolysis products prepared according to Examples 1-6 was determined by titrating an aqueous solution of sodium carbonate containing about 0.2% by weight of hydrolysis product and adjusting the pH to 10 with an aqueous solution of 0.05% calcium acetate until a permanent turbidity formed. The measure of calcin binding capacity indicates how many milligrams of calcium ions per g of hydrolysis product are kept in solution.

The stoichiometric lime-binding capacity of hydrolysis products can be calculated from the following formula:

Atomic weight Ca ____ 20,000 KTV = -2χΕ- ’1000 --E S6- L g - where E denotes the equivalent weight of the hydrolysis product. The latter was determined by asymmetric titration.

The lime binding values of the products according to the invention obtained in the following Table 2 are compared with the corresponding values of polyacrylic acid or poly-9β-hydroxyacrylic acid.

Table 2

Kalkinsitomiskyky

Product E theoretical found

81.1 * 2k6 310 "2" 82.9 21 * 1 1 * 09 "3" 82.8 21 * 2 1 + 25 "1 *" 81.5 21 * 5 U61 * "5" 8U according to Example 1, 5,237,681 * "6" 7U, 7,268,507

Polyacrylic acid 72.3 277 271 *

Poly-N-hydroxyacrylic-82.5 2l * 2 265 acid; .

9,58511

Table 2 shows the superiority of the products according to the invention compared to the reference products in terms of lime-binding capacity; thanks to the former, much more Ca ++ ions remain in solution than the reference substances.

The poly-o-hydroxyacrylic acid, taken as a reference product in Table 2, was prepared as follows: in vacuo at 1 + 0 ° C. The yield of poly -? - chloroacrylic acid was 100% of theory.

b) A saturated aqueous solution of poly-α-chloroacrylic acid was prepared at 30 ° C and this solution was boiled for 2 hours. The precipitated hydrolyzate was washed chloride-free and dried in vacuo at 60 ° C. The yield of poly-o (-hydroxyacrylic acid) was 7T g or 100% of theory. The hydrolyzate had a molecular weight of 2,800 and a lime-binding capacity of 265 mg Ca / g.

c) Neutralization of 25 g of poly-o (hydroxyacrylic acid) with 25 g of 50 ml of sodium hydroxide solution and evaporation of the water gave the sodium salt.

Example 8

In connection with washing experiments, the washing performance of washing solutions was determined in which the concentration of known detergent components was constant, but in which different amounts of building salts A, B or C related to the invention were present; and the results obtained are shown in Figure 1. Structural salts A, B and C refer to the sodium salts of the hydrolysis products prepared according to Examples 1, 3 and 6. For comparison, analogous washing experiments were performed using known structural salts D and E, and the resulting washing power values are also shown in the form of a curve in Figure 1. Structural salt D refers to the sodium salt of polyacrylic acid having a viscosity of * + 0% aqueous solution at 25 ° C at 1900 cP. Structural salt E refers to the sodium salt of poly-4-hydroxyacrylic acid, the preparation of which is described above.

Washing experiments were performed on a standard cotton cloth soiled according to Krefeld in a Launder-O-meter at a wash solution temperature of 95 ° C. Standard fabrics soiled according to Krefeld are defined in: Kurt Lindner, "Tenside, Textilhilfsmittel - Waschrohstoffe", Vissenschaftl. Verlagsgesellschaft Stuttgart (196 ^), Band II, pp. 1Ö37-

According to the German hardness scale, the hardness of the washing water was 20 ° and the pH was 10. The washing time was 30 minutes and the ratio of the washing solution, determined in terms of the product to be washed (kg) and the washing solution (in liters), was 1:50, in the presence of 10 steel balls.

I · 'jo 5 851 1

After the above washing time, the standard cotton cloth was rinsed once with hot and once with cold water of the same hardness and then the degree of whiteness was determined on a Zeiss Elrepho remission photometer using a filter R 53. The washing performance was determined by the separation method obtained from the following equation:% WK »% WG ->? WG g *> where $ WK = washing power- ^ #WG - whiteness of washed material g = whiteness of unwashed material.

The washing experiments were performed with a washing solution having the following composition: 0.5 g / l dodecylbenzenesulfonate 0.15 g / l ethoxylated tallow alcohol with 11 moles of ethylene oxide per mole of alcohol 0.15 g / l hardened tallow soap , 15 g / l magnesium silicate 0.15 g / l sodium silicate 1.25 g / l sodium perborate tetrahydrate 0.5 g / l sodium sulphate 0.05 g / l tylose 0.2-2 g / l structural salt A, B, C, D or E ad 1000 ml of water.

Curves A-E show the washing performance achieved with different washing solutions, where curves A, B and C show the results of washing experiments obtained with structural salts A, B and C according to the invention and curves D and E show the results of washing experiments obtained with known structural salts D and E. These show that, for example, with an amount of structural salt of 1.8 g / l, washing solutions with structural salts A, B and C give a washing efficiency of 35.5% or 3, 1.6% or 3, 1 +%, while under the same conditions with structural salts D and E, the washing efficiency is only 32.6% or 33.0%. These results also show the technical superiority of the aggregates of the invention over known structural salts when the assay is performed using a standard wash test method.

Claims (3)

Detergents with anionic, cationic, zwitterionic, ampholytic and / or non-ionic surfactants and optionally other additives, characterized in that they contain from 10 to 90% by weight of hydroxy-acrylic acid and water-soluble salts of copolymers of acrylic acid having an acrylic acid content of 9 to 85 mol% and having a relative viscosity, measured as a 1 weight solution in a 2N aqueous KaOH solution at 20 ° C, of about 0.05 to about 1.0. Detergents and cleaning agents according to Claim 1, characterized in that the acrylic acid content of the copolymers is from 16 to 50 mol% and the relative viscosity, measured as a 1 wt.% Solution in 2N aqueous NaOH at 20 ° C, is about 0, 1 to 0.8. Detergents according to Claim 1 or 2, characterized in that they contain alkali or ammonium salts of copolymers as structural salts. Detergents according to Claims 1 to 3, characterized in that they preferably contain water-soluble salts of copolymers. -60 weight- #.